---
res:
bibo_abstract:
- An approach to construct vibronically and spin-orbit coupled diabatic potential
energy surfaces (PESs) which describe all three relevant electronic states in
the entrance channels of the X(P) + CH4 -> HX + CH3 reactions (with X= F(P-2),
Cl(P-2), or O(P-3)) is introduced. The diabatization relies on the permutational
symmetry present in the methane molecule and results in diabatic states which
transform as the three p orbitals of the X atom. Spin-orbit coupling is easily
and accurately included using the atomic spin-orbit coupling matrix of the isolated
X atom. The method is applied to the F + CH4 system obtaining an accurate PES
for the entrance channel based on ab initio multireference configuration interaction
(MRCI) calculations. Comparing the resulting PESs with spin-orbit MRCI calculations,
excellent agreement is found for the excited electronic states at all relevant
geometries. The photodetachment spectrum of CH4 center dot F- is investigated
via full-dimensional (12D) quantum dynamics calculations on the coupled PESs using
the multi-layer multi-configurational time-dependent Hartree approach. Extending
previous work [J. Palma and U. Manthe, J. Chem. Phys. 137, 044306 (2012)], which
was restricted to the dynamics on a single adiabatic PES, the contributions of
the electronically excited states to the photodetachment spectrum are calculated
and compared to experiment. Considering different experimental setups, good agreement
between experiment and theory is found. Addressing questions raised in the previous
work, the present dynamical calculations show that the main contribution to the
second peak in the photodetachment spectrum results from electron detachment into
the electronically excited states of the CH4F complex. (C) 2013 AIP Publishing
LLC.@eng
bibo_authorlist:
- autoren_ansetzung:
- Westermann, Till
- Westermann
- Till Westermann
- Westermann, T
- Westermann, T.
- T Westermann
- T. Westermann
foaf_Person:
foaf_givenName: Till
foaf_name: Westermann, Till
foaf_surname: Westermann
foaf_workInfoHomepage: http://www.librecat.org/personId=24758931
- autoren_ansetzung:
- Eisfeld, Wolfgang
- Eisfeld
- Wolfgang Eisfeld
- Eisfeld, W
- Eisfeld, W.
- W Eisfeld
- W. Eisfeld
foaf_Person:
foaf_givenName: Wolfgang
foaf_name: Eisfeld, Wolfgang
foaf_surname: Eisfeld
foaf_workInfoHomepage: http://www.librecat.org/personId=190332
- autoren_ansetzung:
- Manthe, Uwe
- Manthe
- Uwe Manthe
- Manthe, U
- Manthe, U.
- U Manthe
- U. Manthe
foaf_Person:
foaf_givenName: Uwe
foaf_name: Manthe, Uwe
foaf_surname: Manthe
foaf_workInfoHomepage: http://www.librecat.org/personId=109657
bibo_doi: 10.1063/1.4812251
bibo_issue: '1'
bibo_volume: '139'
dct_date: 2013^xs_gYear
dct_identifier:
- UT:000321716400021
dct_isPartOf:
- http://id.crossref.org/issn/0021-9606
dct_language: eng
dct_publisher: AIP Publishing@
dct_title: Coupled potential energy surface for the F(P-2) + CH4 -> HF + CH3 entrance
channel and quantum dynamics of the CH4 center dot F- photodetachment@
fabio_hasPubmedId: '23822305'
...